CA2913121C - Manufacturing method of lithium-titanium composite doped with different metal, and lithium-titanium composite doped with different metal made by same - Google Patents
Manufacturing method of lithium-titanium composite doped with different metal, and lithium-titanium composite doped with different metal made by same Download PDFInfo
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- CA2913121C CA2913121C CA2913121A CA2913121A CA2913121C CA 2913121 C CA2913121 C CA 2913121C CA 2913121 A CA2913121 A CA 2913121A CA 2913121 A CA2913121 A CA 2913121A CA 2913121 C CA2913121 C CA 2913121C
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- lithium
- composite oxide
- titanium composite
- different metals
- oxide doped
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 118
- 239000002184 metal Substances 0.000 title claims abstract description 118
- 239000002131 composite material Substances 0.000 title claims abstract description 100
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 49
- 150000002739 metals Chemical class 0.000 claims abstract description 83
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000010298 pulverizing process Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000001694 spray drying Methods 0.000 claims abstract description 12
- 239000007790 solid phase Substances 0.000 claims abstract description 10
- 229910007848 Li2TiO3 Inorganic materials 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000011734 sodium Substances 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- 238000010304 firing Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 239000011164 primary particle Substances 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000011163 secondary particle Substances 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 claims description 3
- 230000004931 aggregating effect Effects 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 229910011469 Li4/3Ti5/3O4 Inorganic materials 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 abstract description 17
- 239000012535 impurity Substances 0.000 abstract description 6
- 239000007858 starting material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 150000002642 lithium compounds Chemical class 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910012636 LiTi204 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a manufacturing method of a lithium-titanium composite oxide doped with two kinds of different metals and a lithium-titanium composite oxide doped with two kinds of different metals. More particularly, the present invention relates to a manufacturing method of a lithium-titanium composite oxide doped with different metals, solid-phase mixing after adjusting a mixing ratio of two kinds of different metals and pulverizing the same, and spray drying the same to adjust contents of impurities, and a lithium-titanium composite oxide doped with different metals manufactured therefrom.
By doping two kinds of different metals on the surface of the lithium-titanium composite oxide of the present invention after adjusting the ratio of the two different metals to be a desirable ratio, the present invention reduces the contents of rutile-type titanium dioxide, anatase-type titanium dioxide and Li2TiO3 which have been included as impurities in the prior arts, thereby manufacturing titanium dioxide having excellent capacity characteristics and structural characteristics, and a battery including the titanium dioxide having excellent battery characteristics of high initial charge and discharge efficiency and rate capability.
By doping two kinds of different metals on the surface of the lithium-titanium composite oxide of the present invention after adjusting the ratio of the two different metals to be a desirable ratio, the present invention reduces the contents of rutile-type titanium dioxide, anatase-type titanium dioxide and Li2TiO3 which have been included as impurities in the prior arts, thereby manufacturing titanium dioxide having excellent capacity characteristics and structural characteristics, and a battery including the titanium dioxide having excellent battery characteristics of high initial charge and discharge efficiency and rate capability.
Description
, a TITLE OF THE INVENTION
MANUFACTURING METHOD OF LITHIUM-TITANIUM COMPOSITE DOPED
' WITH DIFFERENT METAL, AND LITHIUM-TITANIUM COMPOSITE DOPED
WITH DIFFERENT METAL MADE BY SAME
BACKGROUND OF THE INVENTION
(a) Field of the Invention The present invention relates to a manufacturing method of a lithium-titanium composite oxide doped with different metals, and to a lithium-titanium composite oxide doped with two kinds of different metals. More particularly, the present invention relates to a manufacturing method of a lithium-titanium composite oxide doped with different metals after adjusting a mixing ratio of two kinds of different metals, solid-phase mixing them, pulverizing the same, and spray drying the same to adjust contents of impurities, and a lithium-titanium composite oxide doped with different metals manufactured therefrom.
(b) Description of the Related Art A non-aqueous electrolyte battery charged and discharged by lithium ions moving between negative and positive electrodes is actively researched and developed as a high energy density battery. Recently, a lithium-titanium composite oxide having a high Li intercalation/deintercalation potential has drawn attention. Since lithium metal is not extracted from the lithium-titanium composite oxide during lithium intercalation/deintercalation, the lithium-titanium composite oxide has an advantage of rapid charge and excellent low =
, a temperature performance.
This lithium-titanium composite oxide includes spinet-type lithium titanate represented by a general formula Li (i+x)Ti (2_,00y (x = -0.2 to 1.0 and y =
3 to 4) and may be, for example, Li4,3Ti51304, LiTi204, or Li2TiO3. This material has been conventionally used as a positive active material and may be used as a negative active material, and thus is much expected to continue to be used as a positive and negative electrode active material. This material has a voltage of 1.5 V with a reference to lithium and a long cycle-life. In addition, since expansion and contraction of the material is negligible during the charge-discharge, this material garners attention as an electrode material when a large-scale battery is manufactured. In particular, the spinel-type lithium titanate (represented by U4+115012 (0 5 X 5 3)) has a small volume change during the charge and discharge and excellent reversibility, and thus receives attention.
However, the spinet-type lithium titanate has theoretical capacity of 175 mAhig and thus has a limit in terms of high capacity. In addition, the spinet-type lithium titanate is partially phase-separated into rutile-type TiO2 (r-Ti02) during the manufacturing process.
The rutile-type TiO2 (r-Ti02) has a rock salt structure, and thus has electrochemical activity, but a problem of deteriorating effective capacity of the lithium-titanium composite oxide obtained therefrom due to a low reaction speed, an inclined potential curve, and small capacity occurs.
SUMMARY OF THE INVENTION
In order to solve the problems of the prior arts, the present invention
MANUFACTURING METHOD OF LITHIUM-TITANIUM COMPOSITE DOPED
' WITH DIFFERENT METAL, AND LITHIUM-TITANIUM COMPOSITE DOPED
WITH DIFFERENT METAL MADE BY SAME
BACKGROUND OF THE INVENTION
(a) Field of the Invention The present invention relates to a manufacturing method of a lithium-titanium composite oxide doped with different metals, and to a lithium-titanium composite oxide doped with two kinds of different metals. More particularly, the present invention relates to a manufacturing method of a lithium-titanium composite oxide doped with different metals after adjusting a mixing ratio of two kinds of different metals, solid-phase mixing them, pulverizing the same, and spray drying the same to adjust contents of impurities, and a lithium-titanium composite oxide doped with different metals manufactured therefrom.
(b) Description of the Related Art A non-aqueous electrolyte battery charged and discharged by lithium ions moving between negative and positive electrodes is actively researched and developed as a high energy density battery. Recently, a lithium-titanium composite oxide having a high Li intercalation/deintercalation potential has drawn attention. Since lithium metal is not extracted from the lithium-titanium composite oxide during lithium intercalation/deintercalation, the lithium-titanium composite oxide has an advantage of rapid charge and excellent low =
, a temperature performance.
This lithium-titanium composite oxide includes spinet-type lithium titanate represented by a general formula Li (i+x)Ti (2_,00y (x = -0.2 to 1.0 and y =
3 to 4) and may be, for example, Li4,3Ti51304, LiTi204, or Li2TiO3. This material has been conventionally used as a positive active material and may be used as a negative active material, and thus is much expected to continue to be used as a positive and negative electrode active material. This material has a voltage of 1.5 V with a reference to lithium and a long cycle-life. In addition, since expansion and contraction of the material is negligible during the charge-discharge, this material garners attention as an electrode material when a large-scale battery is manufactured. In particular, the spinel-type lithium titanate (represented by U4+115012 (0 5 X 5 3)) has a small volume change during the charge and discharge and excellent reversibility, and thus receives attention.
However, the spinet-type lithium titanate has theoretical capacity of 175 mAhig and thus has a limit in terms of high capacity. In addition, the spinet-type lithium titanate is partially phase-separated into rutile-type TiO2 (r-Ti02) during the manufacturing process.
The rutile-type TiO2 (r-Ti02) has a rock salt structure, and thus has electrochemical activity, but a problem of deteriorating effective capacity of the lithium-titanium composite oxide obtained therefrom due to a low reaction speed, an inclined potential curve, and small capacity occurs.
SUMMARY OF THE INVENTION
In order to solve the problems of the prior arts, the present invention
2 r , , 4 provides a manufacturing method of a lithium-titanium composite oxide having improved initial capacity and rate capability by doping different metals, .
suppressing generation of anatase and rutile-type titanium dioxide, and controlling sizes of primary particles, and a lithium-titanium composite oxide doped with different metals manufactured by the method.
In order to achieve the purpose, the present invention provides a manufacturing method of a lithium-titanium composite oxide doped with different metals that includes:
i) solid-phase mixing a lithium-containing compound, a titanium oxide, a different metal M-containing compound, and a different metal A-containing compound stoichiometrically;
ii) dispersing the solid-phase mixture of i) in a solvent and wet-pulverizing the mixture to provide particles having an average particle diameter of 0.3 pm to 0.8 pm to prepare a slurry;
iii) spray-drying the slurry to provide particles; and iv) firing the spray-dried particles to manufacture a lithium-titanium composite oxide doped with different metals represented by the following chemical formula.
[Chemical Formula] Li4Ti5_(x+y)MxAy012 (In the chemical formula, the M is selected from the group consisting of Zr, Mg, Al, Ni, Co, Mn, and Cu, the A is selected from the group consisting of Na, K, V, and B, 0.15.x1.5, 05.01, x+y52, and 85x/y59) In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, the different metal M is Zr,
suppressing generation of anatase and rutile-type titanium dioxide, and controlling sizes of primary particles, and a lithium-titanium composite oxide doped with different metals manufactured by the method.
In order to achieve the purpose, the present invention provides a manufacturing method of a lithium-titanium composite oxide doped with different metals that includes:
i) solid-phase mixing a lithium-containing compound, a titanium oxide, a different metal M-containing compound, and a different metal A-containing compound stoichiometrically;
ii) dispersing the solid-phase mixture of i) in a solvent and wet-pulverizing the mixture to provide particles having an average particle diameter of 0.3 pm to 0.8 pm to prepare a slurry;
iii) spray-drying the slurry to provide particles; and iv) firing the spray-dried particles to manufacture a lithium-titanium composite oxide doped with different metals represented by the following chemical formula.
[Chemical Formula] Li4Ti5_(x+y)MxAy012 (In the chemical formula, the M is selected from the group consisting of Zr, Mg, Al, Ni, Co, Mn, and Cu, the A is selected from the group consisting of Na, K, V, and B, 0.15.x1.5, 05.01, x+y52, and 85x/y59) In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, the different metal M is Zr,
3 =
and the different metal A is Na.
In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, the Na-containing compound is selected from the group consisting of sodium carbonate, sodium hydroxide, or sodium carbonate and sodium hydroxide, and sodium hydroxide is preferable because it dissolves in a wet process.
In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, the Zr-containing compound is Zr(OH)4, Zr02, or a mixture thereof.
In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, the titanium oxide is an anatase-type or titanium oxide hydrate.
In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, the lithium-containing compound is lithium hydroxide or lithium carbonate.
In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, in the ii) process, water is used for a solvent, and the wet-pulverizing is performed using zirconia beads at 2000 to 4000 rpm.
In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, in the iii) process, the spray drying is performed while inflowing hot air at a temperature of 250 to 300 C
and discharging hot air at a temperature of 100 to 150 C.
In the manufacturing method of a lithium-titanium composite oxide
and the different metal A is Na.
In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, the Na-containing compound is selected from the group consisting of sodium carbonate, sodium hydroxide, or sodium carbonate and sodium hydroxide, and sodium hydroxide is preferable because it dissolves in a wet process.
In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, the Zr-containing compound is Zr(OH)4, Zr02, or a mixture thereof.
In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, the titanium oxide is an anatase-type or titanium oxide hydrate.
In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, the lithium-containing compound is lithium hydroxide or lithium carbonate.
In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, in the ii) process, water is used for a solvent, and the wet-pulverizing is performed using zirconia beads at 2000 to 4000 rpm.
In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, in the iii) process, the spray drying is performed while inflowing hot air at a temperature of 250 to 300 C
and discharging hot air at a temperature of 100 to 150 C.
In the manufacturing method of a lithium-titanium composite oxide
4 = CA 02913121 2015-11-20 , doped with different metals of the present invention, in the iv) process, the firing is performed by firing the spray-dried resultant of the iii) process under an air atmosphere at 700 to 800 C for 5 h to 10 h.
In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, the method further includes v) pulverizing the fired particles in the iv) process. In the present invention, a dry pulverizing method of the lithium-titanium composite oxide is not particularly limited, but the particles formed by the firing process are preferably pulverized to a microsize, specifically using a jet air mill.
The present invention provides a lithium-titanium composite oxide doped with two kinds of different metals that is manufactured by the dry pulverizing method, represented by the chemical formula, having a spinel structure, and including secondary particles formed by aggregating primary particles, wherein a diameter of the primary particles ranges from 0.2 pm to 0.6 pm and a diameter of the secondary particles ranges from 5 pm to 25 pm.
[Chemical Formula] Li4Ti5_(0y)MxAy012 (In the chemical formula, the M is selected from the group consisting of Zr, Mg, Al, Ni, Co, Mn, and Cu, the A is selected from the group consisting of Na, K, V, and B, 0.15)(51.5, 05.y51, x+02, and 85x/y59) The lithium-titanium composite oxide doped with two kinds of different metals of the present invention has a main peak intensity of anatase-type TiO2 of less than or equal to 1, a main peak intensity of R-Ti02 of less than or equal to 1, and a main peak intensity of Li2TiO3 of less than or equal to 5 when a main peak intensity of Li4/3Ti5/304 is 100.
In the manufacturing method of a lithium-titanium composite oxide doped with different metals of the present invention, the method further includes v) pulverizing the fired particles in the iv) process. In the present invention, a dry pulverizing method of the lithium-titanium composite oxide is not particularly limited, but the particles formed by the firing process are preferably pulverized to a microsize, specifically using a jet air mill.
The present invention provides a lithium-titanium composite oxide doped with two kinds of different metals that is manufactured by the dry pulverizing method, represented by the chemical formula, having a spinel structure, and including secondary particles formed by aggregating primary particles, wherein a diameter of the primary particles ranges from 0.2 pm to 0.6 pm and a diameter of the secondary particles ranges from 5 pm to 25 pm.
[Chemical Formula] Li4Ti5_(0y)MxAy012 (In the chemical formula, the M is selected from the group consisting of Zr, Mg, Al, Ni, Co, Mn, and Cu, the A is selected from the group consisting of Na, K, V, and B, 0.15)(51.5, 05.y51, x+02, and 85x/y59) The lithium-titanium composite oxide doped with two kinds of different metals of the present invention has a main peak intensity of anatase-type TiO2 of less than or equal to 1, a main peak intensity of R-Ti02 of less than or equal to 1, and a main peak intensity of Li2TiO3 of less than or equal to 5 when a main peak intensity of Li4/3Ti5/304 is 100.
5 The present invention provides a positive electrode including the lithium-titanium composite oxide doped with different metals of the present invention as a positive active material, or a negative electrode including the lithium-titanium composite oxide doped with different metals of the present invention as a negative active material.
The present invention provides a rechargeable lithium battery including a positive electrode including the lithium-titanium composite oxide doped with different metals of the present invention as a positive active material, or a rechargeable lithium battery including a negative electrode including the lithium-titanium composite oxide doped with different metals of the present invention as a negative active material.
Hereinafter, the present invention is described in detail.
The present invention provides a method of manufacturing the lithium-titanium composite oxide by simultaneously solid-phase mixing a lithium compound and a titanium compound as raw compounds and a different metal-containing compound for doping the raw compound with two kinds of different metals, and adjusting a ratio of the two kinds of different metals-containing compounds.
The titanium oxide-containing compound as a starting material may be any of a chloride, a sulfate, an organic salt, and the like. However, the titanium oxide-containing compound as a starting material may have a crystal structure such as anatase-type titanium dioxide or titanium oxide hydrate in order to manufacture a lithium-titanium composite oxide having excellent discharge capacity or battery characteristics as starting materials.
The present invention provides a rechargeable lithium battery including a positive electrode including the lithium-titanium composite oxide doped with different metals of the present invention as a positive active material, or a rechargeable lithium battery including a negative electrode including the lithium-titanium composite oxide doped with different metals of the present invention as a negative active material.
Hereinafter, the present invention is described in detail.
The present invention provides a method of manufacturing the lithium-titanium composite oxide by simultaneously solid-phase mixing a lithium compound and a titanium compound as raw compounds and a different metal-containing compound for doping the raw compound with two kinds of different metals, and adjusting a ratio of the two kinds of different metals-containing compounds.
The titanium oxide-containing compound as a starting material may be any of a chloride, a sulfate, an organic salt, and the like. However, the titanium oxide-containing compound as a starting material may have a crystal structure such as anatase-type titanium dioxide or titanium oxide hydrate in order to manufacture a lithium-titanium composite oxide having excellent discharge capacity or battery characteristics as starting materials.
6 = CA 02913121 2015-11-20 The anatase-type titanium dioxide needs to have purity of greater than or equal to 95 %, or greater than or equal to 98 %. When the purity is less than 95 %, capacity per weight of an active material is deteriorated. For example, the anatase-type titanium dioxide having high purity of 99.99 % may be used, but it is expensive. When the anatase-type titanium dioxide has purity of greater than or equal to 98 %, the influence of high purity in terms of an electrode active material becomes smaller than an influence on a particle diameter and a particle shape.
In the lithium compound in the manufacturing method of the present invention, a starting material may be a lithium salt such as lithium hydroxide, lithium hydroxide monohydrate, lithium oxide, lithium hydrogen carbonate, or lithium carbonate.
In the manufacturing method of the present invention, the different metal M of the doped two kinds of different metals is selected from the group consisting of Zr, Mg, Al, Ni, Co, Mn, and Cu, while the different metal A is selected from the group consisting of Na, K, V, and B, and it is preferable that Zr and Na are simultaneously doped in terms of capacity characteristics and structural characteristics.
The Na-containing compound is preferably sodium hydroxide, sodium carbonate, or a mixture thereof. The Zr-containing compound is preferably Zr(OH)4, Zr02, or a mixture thereof.
In the present invention, the different metal M may be doped in an amount of greater than or equal to 0.1 % and less than or equal to 1.5 %, while the different metal A may be doped in a range of 0 % to 1 %, and herein, the
In the lithium compound in the manufacturing method of the present invention, a starting material may be a lithium salt such as lithium hydroxide, lithium hydroxide monohydrate, lithium oxide, lithium hydrogen carbonate, or lithium carbonate.
In the manufacturing method of the present invention, the different metal M of the doped two kinds of different metals is selected from the group consisting of Zr, Mg, Al, Ni, Co, Mn, and Cu, while the different metal A is selected from the group consisting of Na, K, V, and B, and it is preferable that Zr and Na are simultaneously doped in terms of capacity characteristics and structural characteristics.
The Na-containing compound is preferably sodium hydroxide, sodium carbonate, or a mixture thereof. The Zr-containing compound is preferably Zr(OH)4, Zr02, or a mixture thereof.
In the present invention, the different metal M may be doped in an amount of greater than or equal to 0.1 % and less than or equal to 1.5 %, while the different metal A may be doped in a range of 0 % to 1 %, and herein, the
7 = CA 02913121 2015-11-20 . .
different metal M and the different metal A may be doped in a total amount of less than or equal to 2 % and in a ratio of the doping amount x of the different metal M relative to the doping amount y of the different metal A satisfying 85 x/y 59.
When the different metal M is doped in an amount of greater than 1.5 %, conductivity may be rather deteriorated, and overall performance of a battery may be deteriorated, and when the different metal A is doped in an amount of 0 wt%, an effect of improving battery safety due to doping of the different metals may be insignificant.
The method of a lithium-titanium composite oxide according to the present invention provides an assembled powder of a secondary particle formed by aggregation of primary particles by mixing a lithium compound, a titanium compound, and a doping metal as starting materials stoichiometrically, dispersing a solid-phase mixture in a liquid medium, wet-pulverizing to prepare a slurry and spray-drying the slurry and firing the resultant using a known method.
In the manufacturing method of the present invention, the simultaneously-mixed lithium compound, titanium compound, and doping metal are dispersed in a dispersion medium and then wet-pulverized by using a medium-stirring type of grinder and the like. The dispersion medium used for wet-pulverizing slurry may be various organic solvents and aqueous solvents, but specifically may be water. The raw compounds may be used in an amount of greater than or equal to 50 wt% and less than or equal to 60 wt% based on the total weight of the slurry. When the weight ratio is less than the range, the
different metal M and the different metal A may be doped in a total amount of less than or equal to 2 % and in a ratio of the doping amount x of the different metal M relative to the doping amount y of the different metal A satisfying 85 x/y 59.
When the different metal M is doped in an amount of greater than 1.5 %, conductivity may be rather deteriorated, and overall performance of a battery may be deteriorated, and when the different metal A is doped in an amount of 0 wt%, an effect of improving battery safety due to doping of the different metals may be insignificant.
The method of a lithium-titanium composite oxide according to the present invention provides an assembled powder of a secondary particle formed by aggregation of primary particles by mixing a lithium compound, a titanium compound, and a doping metal as starting materials stoichiometrically, dispersing a solid-phase mixture in a liquid medium, wet-pulverizing to prepare a slurry and spray-drying the slurry and firing the resultant using a known method.
In the manufacturing method of the present invention, the simultaneously-mixed lithium compound, titanium compound, and doping metal are dispersed in a dispersion medium and then wet-pulverized by using a medium-stirring type of grinder and the like. The dispersion medium used for wet-pulverizing slurry may be various organic solvents and aqueous solvents, but specifically may be water. The raw compounds may be used in an amount of greater than or equal to 50 wt% and less than or equal to 60 wt% based on the total weight of the slurry. When the weight ratio is less than the range, the
8 slurry has an extremely thin concentration, and spherically-shaped particles obtained through the spray-drying may become unnecessarily small or be easily broken. When the weight ratio is greater than the range, it may be difficult to maintain uniformity of the slurry.
The wet-pulverization may be performed at 2000 to 4000 rpm, so that a solid in the slurry may have an average particle diameter (D50) ranging from 0.3 pm to 0.8 pm. When the solid in the slurry has too large an average particle diameter, sphericity as well as reactivity may be deteriorated during the firing process, and thus charge density of a final powder tends to be deteriorated.
However, when the slurry is more than necessarily pulverized, the pulverization cost is increased, and thus the slurry may be wet-pulverized until the average particle diameter ranges from 0.3 pm to 0.8 pm.
Then, the lithium-titanium composite oxide powder of the present invention may be spray-dried to bond primary particles and form secondary particles, and herein, the primary particles may have a diameter ranging from 0.3 pm to 0.7 pm and the secondary particles may have a diameter ranging from 5 pm to 25 pm.
The spraying may be performed by pressing a nozzle having a predetermined hole size but using any commonly-used spray-drying equipment without a particular limit. In general, a sprayer is classified into a rotating disc type and a nozzle type, and the nozzle type of sprayer is classified into a pressure nozzle and a two-fluid nozzle. In addition, the sprayer may include any well-known equipment in a related field such as a rotary sprayer, a pressure nozzle, an air nozzle, a sonic nozzle, and the like. The spray equipment may
The wet-pulverization may be performed at 2000 to 4000 rpm, so that a solid in the slurry may have an average particle diameter (D50) ranging from 0.3 pm to 0.8 pm. When the solid in the slurry has too large an average particle diameter, sphericity as well as reactivity may be deteriorated during the firing process, and thus charge density of a final powder tends to be deteriorated.
However, when the slurry is more than necessarily pulverized, the pulverization cost is increased, and thus the slurry may be wet-pulverized until the average particle diameter ranges from 0.3 pm to 0.8 pm.
Then, the lithium-titanium composite oxide powder of the present invention may be spray-dried to bond primary particles and form secondary particles, and herein, the primary particles may have a diameter ranging from 0.3 pm to 0.7 pm and the secondary particles may have a diameter ranging from 5 pm to 25 pm.
The spraying may be performed by pressing a nozzle having a predetermined hole size but using any commonly-used spray-drying equipment without a particular limit. In general, a sprayer is classified into a rotating disc type and a nozzle type, and the nozzle type of sprayer is classified into a pressure nozzle and a two-fluid nozzle. In addition, the sprayer may include any well-known equipment in a related field such as a rotary sprayer, a pressure nozzle, an air nozzle, a sonic nozzle, and the like. The spray equipment may
9 =
be selected typically considering a supply speed, viscosity of a supply, a desired particle size of a spray-dried product, dispersion, a droplet size of a water-in-oil emulsion or a water-in-oil microemulsion, and the like.
In the step iii) of spray-drying the slurry of the step ii), a charge hot air temperature may be set at about to 250 to 300 C, while a discharge hot air temperature may be set at 100 to 150 C to improve a particle shape, a particle size, and crystallinity.
Then, a mixed powder obtained in this way is fired. The firing may be performed at greater than or equal to 600 C, greater than or equal to 700 C, in general greater than or equal to 900 C, but specifically, greater than or equal to 800 C depending on a kind of lithium compound and titanium oxide, metal compound such as different metals and the like, and the like, as a raw compound. Herein, the firing may be controlled depending on the composition of the raw compound, but when performed at too high a temperature, a primary particle may overgrow, while when performed at too low a temperature, volume density becomes small, and a specific surface area becomes extremely large.
The firing may be performed for different times depending on a temperature, but for greater than or equal to 30 min, greater than or equal to 5 h, but commonly greater than or equal to 20 h, and specifically, less than or equal to 10 h within the aforementioned temperature range. When the firing is performed for too short a time, a lithium-titanium composite oxide powder having excellent crystallinity is difficult to obtain, while when performed for too long a time, it is not p[particularly practical. In addition, when performed for too long a time, the lithium-titanium composite oxide powder needs to be pulverized = CA 02913121 2015-11-20 or is difficult to crush, and thus the firing may be performed for less than or equal to 10 h.
The firing may be performed under an air atmosphere, or under an inert gas atmosphere such as nitrogen, argon, or the like depending on the composition or structure of a manufactured compound. The resultant is preferably pressed.
The method of manufacturing a lithium-titanium composite oxide doped with different metals according to the present invention may further include a step v) of pulverizing the fired particles. The fired particles may be pulverized in a dry pulverizing method, and the dry pulverization has no particular limit but may specifically be performed by using a jet air mill to have a micrometer size.
Another embodiment of the present invention provides particles pulverized by the additional dry-pulverizing step. In the present invention, the particles are primary particles and have a weaker bond through the dry pulverization and separation, and resultantly have a particle size D50 ranging from 0.7 pm to 1.5 pm.
The present invention provides a lithium-titanium composite oxide doped with different metals manufactured by the manufacturing method according to the present invention and represented by the following chemical formula.
[Chemical Formula] Li4Ti5_(0y)MAy012 (In the chemical formula, M is selected from the group consisting of Zr, Mg, Al, Ni, Co, Mn, and Cu, the A is selected from the group consisting of Na, K, V, and B, 0.15x51.5, 05y5.1, x+y.52, and 85x/y59) Each component of the lithium-titanium composite oxide doped with different metals synthesized in the present invention may have a composition adjusted by a ratio of each compound during the mixing, that is, a ratio of mixing of each compound. In addition, powder characteristics such as particle distribution, BET specific surface area, tap density, and pulverized powder density may be adjusted by a mixing method and an oxidation treatment.
The lithium-titanium composite oxide doped with different metals of the present invention includes secondary particles formed by aggregation of primary particles, wherein a diameter of the primary particles ranges from 0.5 pm to 0.8 pm and a diameter of the secondary particles ranges from 5 pm to 25 pm.
The lithium-titanium composite oxide doped with different metals manufactured according to the manufacturing method of the present invention has a spine! structure. Particularly, the lithium-titanium composite oxide doped with different metals manufactured according to the manufacturing method of the present invention has a main peak intensity of anatase-type TiO2 of less than or equal to 1, a main peak intensity of R-Ti02 of less than or equal to 1, and a main peak intensity of Li2TiO3 of less than or equal to 5 when a main peak intensity of Li4/3Ti5/304 is 100.
The rutile-type titanium dioxide may show a main peak at 20 = 27.4.
The lithium-titanium composite oxide doped with different metals manufactured in the manufacturing method of the present invention includes the rutile-type titanium dioxide that deteriorates capacity as an impurity but shows a main peak size of less than or equal to 1 and is thus included in a very small amount, and accordingly, may increase battery capacity as well as crystallinity.
The method of manufacturing the lithium-titanium composite oxide doped with different metals according to the present invention may provide a titanium dioxide having excellent capacity characteristics and structural characteristics by mixing, pulverizing, and spray-drying different metals to dope two kinds of different metals on the surface of a lithium-titanium composite oxide in an appropriate ratio and reduce the content of conventional impurities such as rutile-type titanium dioxide, anatase-type titanium dioxide, and Li2TiO3, and accordingly, a battery including the titanium dioxide doped with different metals shows excellent battery characteristics such as high initial charge and discharge efficiency and rate capability.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a SEM photograph showing a lithium-titanium composite oxide doped with one kind of different metal according to one example of the present invention.
FIG. 2 shows capacity characteristics and rate capabilities of a test cell including the lithium-titanium composite oxide doped with one kind of a different metal according to one example of the present invention.
FIG. 3 is a SEM photograph showing a lithium-titanium composite oxide doped with two kinds of different metals according to one example of the present invention.
FIG. 4 shows capacity characteristics and rate capabilities of a test cell including the lithium-titanium composite oxide doped with two kinds of different metals according to one example of the present invention.
FIG. 5 shows capacity characteristics and rate capabilities of a test cell including the lithium-titanium composite oxide doped with two kind of a different metal according to one example of the present invention.
FIG. 6 is an XRD photograph showing the lithium-titanium composite oxide doped with two kinds of different metals according to one example of the present invention and a lithium-titanium composite oxide according to a comparative example.
DETAILED DESCRIPTION
Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, and this disclosure is not limited thereto.
<Example 1> Manufacture of Lithium-Titanium Composite Oxide Doped with One Kind of a Different Metal One mol of lithium hydroxide and 1 mol of an anatase-type titanium oxide as a starting material are mixed with 0.1 mol of Zr as a different metal in a solid-phase, and they are then stirred and dissolved in water.
Next, a lithium-titanium composite oxide was manufactured by pulverizing the mixture using zirconia beads at 3000 rpm, spray-drying them at a hot air temperature of 270 C and at a discharge hot air temperature of 120 C, heat-treating them at two firing temperatures of 750 C and 770 C for 10 hours under an oxygen atmosphere, and dry-pulverizing them with a jet air mill.
Then, Al, Mg, and Na as different metals were respectively used in a ratio of 0.05 mol to manufacture each lithium-titanium composite oxide in the same method as above.
<Experimental Example 1-1> Measurement of SEM Photograph FIG. 1 shows a SEM photograph showing each lithium-titanium composite oxide doped with one kind of a different metal according to Example I.
<Experimental Examples 1 and 2> Evaluation of Battery Characteristics ¨
Measurement of Capacity Characteristics and Rate Capability The lithium-titanium composite oxide doped with one kind of a different metal according to Example 1 as a positive active material, a lithium foil as a counter electrode, and a porous polyethylene film (Celgard 2300 made by Celgard, LLC, thickness: 25 pm) as a separator, and a liquid electrolyte solution obtained by mixing ethylene carbonate and dimethyl carbonate in a volume ratio of 1:2 and dissolving L1PF6 in a concentration of 1 mol in the mixed solvent were used according to a commonly-known method, manufacturing a coin cell. A
coin cell according to the comparative example was manufactured according to the same method as above.
The capacity and rate capability of the test cell according to Comparative Example 1 including a lithium-titanium composite oxide doped with one kind of a different metal were measured, and the results are provided in FIG. 2. Referring to FIG. 2, the lithium-titanium composite oxide doped with Zr or Na turned out to improve the capacity characteristic and rate capability compared with the lithium-titanium composite oxide doped with Al or Mg.
<Example 2> Manufacture of Lithium-titanium Composite Oxide Doped with Two Kinds of Different Metals Each lithium-titanium composite oxide doped with two kinds of different metals such as zirconium and sodium which showed an excellent capacity characteristic and rate capability in Example 1 was manufactured.
Firstly, 1 nnol of lithium hydroxide and 1 mol of anatase-type titanium oxide, and 0.05 mol of zirconium as a starting material, were mixed in a solid phase with a mixture of sodium carbonate and sodium hydroxide as a sodium , , compound by changing their mol ratios to 0.006, 0.008, and 0.01, and the mixture was stirred and dissolved in water.
The solution was wet-pulverized with zirconia beads at 3000 rpm, spray-dried at a hot-air temperature of 270 C and at a discharge hot-air temperature of 120 C, respectively heat-treated at 750 C and 770 C for 10 h under an oxygen atmosphere, and dry-ground with a jet air mill, manufacturing a lithium-titanium composite oxide doped with two kinds of different metals.
<Experimental Example 2-1> SEM Photograph Measurement SEM photographs of particles of the lithium-titanium composite oxide doped with two kinds of different metals according to Example 2 and a lithium-titanium composite oxide doped with only Zr in an amount of 0.05 mol are provided in FIG. 3. When two kinds of different metals were doped in FIG. 3, the particle size was not changed.
FIG. 4 shows the results of the primary particle size of the lithium-titanium composite oxide doped with two kinds of different metals according to Example 2. The primary particle size was in a range of 0.564 to 0.757 urn.
<Experimental Example 2-2> Electrochemical Characteristics The lithium-titanium composite oxide doped with two kinds of different metals according to Example 2 as a positive active material, a lithium foil as a counter electrode, a porous polyethylene film (thickness: 25 pm, Celgard 2300, Celgard LLC.) as a separator, and a liquid electrolyte solution prepared by mixing ethylene carbonate and dimethyl carbonate in a volume ratio of 1:2 and dissolving LiPF6 in a concentration of 1 mol were used to manufacture a coin cell in a commonly-known method. A coin cell according to the comparative . .
example was manufactured according to the same method as above.
The capacity and rate capability of a test cell including the lithium-titanium composite oxide doped with two kinds of different metals according to Example 2 were measured, and the results are provided in FIG. 5. Referring to FIG. 5, the cells using lithium-titanium composite oxides respectively doped with two kinds of different metals of Zr and Na in an amount of 0.05 mol and 0.006 mol and heat-treating them at 750 C according to the examples showed superior improvement rate capabilities compared with the cell using the lithium-titanium composite oxide according to the comparative example.
<Experimental Example 2-3> XRD Measurement FIG. 6 shows the lithium-titanium composite oxides respectively doped with two kinds of different metals of Zr and Na in an amount of 0.05 mol and 0.006 mol and heat-treated at 750 C according to the examples and the lithium-titanium composite oxide not doped with different metals according to the comparative example.
Referring to FIG. 6, the lithium-titanium composite oxides doped with two kinds of different metals of Na and Zr according to one example of the present invention had a spinel structure, and when Li4/3Ti5/304 has a main peak intensity of 100, anatase-type TiO2 had a main peak intensity of less than or equal to 1, rutile-type TiO2 had a main peak intensity of less than or equal to 1, and Li2TiO3 had main peak intensity of less than or equal to 5. Battery performance turned out to be improved by controlling the content of impurities such as anatase-type titanium dioxide, rutile-type titanium dioxide, and Li2TiO3 doped with the Na and Zr as different metals and the like.
be selected typically considering a supply speed, viscosity of a supply, a desired particle size of a spray-dried product, dispersion, a droplet size of a water-in-oil emulsion or a water-in-oil microemulsion, and the like.
In the step iii) of spray-drying the slurry of the step ii), a charge hot air temperature may be set at about to 250 to 300 C, while a discharge hot air temperature may be set at 100 to 150 C to improve a particle shape, a particle size, and crystallinity.
Then, a mixed powder obtained in this way is fired. The firing may be performed at greater than or equal to 600 C, greater than or equal to 700 C, in general greater than or equal to 900 C, but specifically, greater than or equal to 800 C depending on a kind of lithium compound and titanium oxide, metal compound such as different metals and the like, and the like, as a raw compound. Herein, the firing may be controlled depending on the composition of the raw compound, but when performed at too high a temperature, a primary particle may overgrow, while when performed at too low a temperature, volume density becomes small, and a specific surface area becomes extremely large.
The firing may be performed for different times depending on a temperature, but for greater than or equal to 30 min, greater than or equal to 5 h, but commonly greater than or equal to 20 h, and specifically, less than or equal to 10 h within the aforementioned temperature range. When the firing is performed for too short a time, a lithium-titanium composite oxide powder having excellent crystallinity is difficult to obtain, while when performed for too long a time, it is not p[particularly practical. In addition, when performed for too long a time, the lithium-titanium composite oxide powder needs to be pulverized = CA 02913121 2015-11-20 or is difficult to crush, and thus the firing may be performed for less than or equal to 10 h.
The firing may be performed under an air atmosphere, or under an inert gas atmosphere such as nitrogen, argon, or the like depending on the composition or structure of a manufactured compound. The resultant is preferably pressed.
The method of manufacturing a lithium-titanium composite oxide doped with different metals according to the present invention may further include a step v) of pulverizing the fired particles. The fired particles may be pulverized in a dry pulverizing method, and the dry pulverization has no particular limit but may specifically be performed by using a jet air mill to have a micrometer size.
Another embodiment of the present invention provides particles pulverized by the additional dry-pulverizing step. In the present invention, the particles are primary particles and have a weaker bond through the dry pulverization and separation, and resultantly have a particle size D50 ranging from 0.7 pm to 1.5 pm.
The present invention provides a lithium-titanium composite oxide doped with different metals manufactured by the manufacturing method according to the present invention and represented by the following chemical formula.
[Chemical Formula] Li4Ti5_(0y)MAy012 (In the chemical formula, M is selected from the group consisting of Zr, Mg, Al, Ni, Co, Mn, and Cu, the A is selected from the group consisting of Na, K, V, and B, 0.15x51.5, 05y5.1, x+y.52, and 85x/y59) Each component of the lithium-titanium composite oxide doped with different metals synthesized in the present invention may have a composition adjusted by a ratio of each compound during the mixing, that is, a ratio of mixing of each compound. In addition, powder characteristics such as particle distribution, BET specific surface area, tap density, and pulverized powder density may be adjusted by a mixing method and an oxidation treatment.
The lithium-titanium composite oxide doped with different metals of the present invention includes secondary particles formed by aggregation of primary particles, wherein a diameter of the primary particles ranges from 0.5 pm to 0.8 pm and a diameter of the secondary particles ranges from 5 pm to 25 pm.
The lithium-titanium composite oxide doped with different metals manufactured according to the manufacturing method of the present invention has a spine! structure. Particularly, the lithium-titanium composite oxide doped with different metals manufactured according to the manufacturing method of the present invention has a main peak intensity of anatase-type TiO2 of less than or equal to 1, a main peak intensity of R-Ti02 of less than or equal to 1, and a main peak intensity of Li2TiO3 of less than or equal to 5 when a main peak intensity of Li4/3Ti5/304 is 100.
The rutile-type titanium dioxide may show a main peak at 20 = 27.4.
The lithium-titanium composite oxide doped with different metals manufactured in the manufacturing method of the present invention includes the rutile-type titanium dioxide that deteriorates capacity as an impurity but shows a main peak size of less than or equal to 1 and is thus included in a very small amount, and accordingly, may increase battery capacity as well as crystallinity.
The method of manufacturing the lithium-titanium composite oxide doped with different metals according to the present invention may provide a titanium dioxide having excellent capacity characteristics and structural characteristics by mixing, pulverizing, and spray-drying different metals to dope two kinds of different metals on the surface of a lithium-titanium composite oxide in an appropriate ratio and reduce the content of conventional impurities such as rutile-type titanium dioxide, anatase-type titanium dioxide, and Li2TiO3, and accordingly, a battery including the titanium dioxide doped with different metals shows excellent battery characteristics such as high initial charge and discharge efficiency and rate capability.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a SEM photograph showing a lithium-titanium composite oxide doped with one kind of different metal according to one example of the present invention.
FIG. 2 shows capacity characteristics and rate capabilities of a test cell including the lithium-titanium composite oxide doped with one kind of a different metal according to one example of the present invention.
FIG. 3 is a SEM photograph showing a lithium-titanium composite oxide doped with two kinds of different metals according to one example of the present invention.
FIG. 4 shows capacity characteristics and rate capabilities of a test cell including the lithium-titanium composite oxide doped with two kinds of different metals according to one example of the present invention.
FIG. 5 shows capacity characteristics and rate capabilities of a test cell including the lithium-titanium composite oxide doped with two kind of a different metal according to one example of the present invention.
FIG. 6 is an XRD photograph showing the lithium-titanium composite oxide doped with two kinds of different metals according to one example of the present invention and a lithium-titanium composite oxide according to a comparative example.
DETAILED DESCRIPTION
Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, and this disclosure is not limited thereto.
<Example 1> Manufacture of Lithium-Titanium Composite Oxide Doped with One Kind of a Different Metal One mol of lithium hydroxide and 1 mol of an anatase-type titanium oxide as a starting material are mixed with 0.1 mol of Zr as a different metal in a solid-phase, and they are then stirred and dissolved in water.
Next, a lithium-titanium composite oxide was manufactured by pulverizing the mixture using zirconia beads at 3000 rpm, spray-drying them at a hot air temperature of 270 C and at a discharge hot air temperature of 120 C, heat-treating them at two firing temperatures of 750 C and 770 C for 10 hours under an oxygen atmosphere, and dry-pulverizing them with a jet air mill.
Then, Al, Mg, and Na as different metals were respectively used in a ratio of 0.05 mol to manufacture each lithium-titanium composite oxide in the same method as above.
<Experimental Example 1-1> Measurement of SEM Photograph FIG. 1 shows a SEM photograph showing each lithium-titanium composite oxide doped with one kind of a different metal according to Example I.
<Experimental Examples 1 and 2> Evaluation of Battery Characteristics ¨
Measurement of Capacity Characteristics and Rate Capability The lithium-titanium composite oxide doped with one kind of a different metal according to Example 1 as a positive active material, a lithium foil as a counter electrode, and a porous polyethylene film (Celgard 2300 made by Celgard, LLC, thickness: 25 pm) as a separator, and a liquid electrolyte solution obtained by mixing ethylene carbonate and dimethyl carbonate in a volume ratio of 1:2 and dissolving L1PF6 in a concentration of 1 mol in the mixed solvent were used according to a commonly-known method, manufacturing a coin cell. A
coin cell according to the comparative example was manufactured according to the same method as above.
The capacity and rate capability of the test cell according to Comparative Example 1 including a lithium-titanium composite oxide doped with one kind of a different metal were measured, and the results are provided in FIG. 2. Referring to FIG. 2, the lithium-titanium composite oxide doped with Zr or Na turned out to improve the capacity characteristic and rate capability compared with the lithium-titanium composite oxide doped with Al or Mg.
<Example 2> Manufacture of Lithium-titanium Composite Oxide Doped with Two Kinds of Different Metals Each lithium-titanium composite oxide doped with two kinds of different metals such as zirconium and sodium which showed an excellent capacity characteristic and rate capability in Example 1 was manufactured.
Firstly, 1 nnol of lithium hydroxide and 1 mol of anatase-type titanium oxide, and 0.05 mol of zirconium as a starting material, were mixed in a solid phase with a mixture of sodium carbonate and sodium hydroxide as a sodium , , compound by changing their mol ratios to 0.006, 0.008, and 0.01, and the mixture was stirred and dissolved in water.
The solution was wet-pulverized with zirconia beads at 3000 rpm, spray-dried at a hot-air temperature of 270 C and at a discharge hot-air temperature of 120 C, respectively heat-treated at 750 C and 770 C for 10 h under an oxygen atmosphere, and dry-ground with a jet air mill, manufacturing a lithium-titanium composite oxide doped with two kinds of different metals.
<Experimental Example 2-1> SEM Photograph Measurement SEM photographs of particles of the lithium-titanium composite oxide doped with two kinds of different metals according to Example 2 and a lithium-titanium composite oxide doped with only Zr in an amount of 0.05 mol are provided in FIG. 3. When two kinds of different metals were doped in FIG. 3, the particle size was not changed.
FIG. 4 shows the results of the primary particle size of the lithium-titanium composite oxide doped with two kinds of different metals according to Example 2. The primary particle size was in a range of 0.564 to 0.757 urn.
<Experimental Example 2-2> Electrochemical Characteristics The lithium-titanium composite oxide doped with two kinds of different metals according to Example 2 as a positive active material, a lithium foil as a counter electrode, a porous polyethylene film (thickness: 25 pm, Celgard 2300, Celgard LLC.) as a separator, and a liquid electrolyte solution prepared by mixing ethylene carbonate and dimethyl carbonate in a volume ratio of 1:2 and dissolving LiPF6 in a concentration of 1 mol were used to manufacture a coin cell in a commonly-known method. A coin cell according to the comparative . .
example was manufactured according to the same method as above.
The capacity and rate capability of a test cell including the lithium-titanium composite oxide doped with two kinds of different metals according to Example 2 were measured, and the results are provided in FIG. 5. Referring to FIG. 5, the cells using lithium-titanium composite oxides respectively doped with two kinds of different metals of Zr and Na in an amount of 0.05 mol and 0.006 mol and heat-treating them at 750 C according to the examples showed superior improvement rate capabilities compared with the cell using the lithium-titanium composite oxide according to the comparative example.
<Experimental Example 2-3> XRD Measurement FIG. 6 shows the lithium-titanium composite oxides respectively doped with two kinds of different metals of Zr and Na in an amount of 0.05 mol and 0.006 mol and heat-treated at 750 C according to the examples and the lithium-titanium composite oxide not doped with different metals according to the comparative example.
Referring to FIG. 6, the lithium-titanium composite oxides doped with two kinds of different metals of Na and Zr according to one example of the present invention had a spinel structure, and when Li4/3Ti5/304 has a main peak intensity of 100, anatase-type TiO2 had a main peak intensity of less than or equal to 1, rutile-type TiO2 had a main peak intensity of less than or equal to 1, and Li2TiO3 had main peak intensity of less than or equal to 5. Battery performance turned out to be improved by controlling the content of impurities such as anatase-type titanium dioxide, rutile-type titanium dioxide, and Li2TiO3 doped with the Na and Zr as different metals and the like.
Claims (19)
1. A manufacturing method of a lithium-titanium composite oxide doped with different metals, comprising:
i) solid-phase stoichiometrically mixing a lithium-containing compound, a titanium oxide, a different metal M-containing compound, and a different metal A-containing compound;
ii) dispersing the solid-phase mixture of the i) in a solvent and wet-pulverizing the mixture to have particles having an average particle diameter of 0.3 µm to 0.8 µm to prepare a slurry;
iii) spray-drying the slurry to provide particles; and iv) firing the spray-dried particles to manufacture a lithium-titanium composite oxide doped with different metals represented by the following chemical formula:
[Chemical Formula] Li4Ti5-(x+y)MxAyO12 in the chemical formula, the M is selected from the group consisting of Zr, Mg, Al, Ni, Co, Mn, and Cu, the A is selected from the group consisting of Na, K, and B, 0.1<= x <=1.5, 0<y<=1, x+y<=2, and 8<=x/y <=9.
i) solid-phase stoichiometrically mixing a lithium-containing compound, a titanium oxide, a different metal M-containing compound, and a different metal A-containing compound;
ii) dispersing the solid-phase mixture of the i) in a solvent and wet-pulverizing the mixture to have particles having an average particle diameter of 0.3 µm to 0.8 µm to prepare a slurry;
iii) spray-drying the slurry to provide particles; and iv) firing the spray-dried particles to manufacture a lithium-titanium composite oxide doped with different metals represented by the following chemical formula:
[Chemical Formula] Li4Ti5-(x+y)MxAyO12 in the chemical formula, the M is selected from the group consisting of Zr, Mg, Al, Ni, Co, Mn, and Cu, the A is selected from the group consisting of Na, K, and B, 0.1<= x <=1.5, 0<y<=1, x+y<=2, and 8<=x/y <=9.
2. The manufacturing method of a lithium-titanium composite oxide doped with different metals of claim 1, wherein the different metal M is Zr and the different metal A is Na.
3. The manufacturing method of a lithium-titanium composite oxide doped with different metals of claim 2, wherein the Zr-containing compound is Zr(OH)4, ZrO2, or a mixture thereof
4. The manufacturing method of a lithium-titanium composite oxide doped with different metals of claim 2, wherein the Na-containing compound is selected from the group consisting of sodium carbonate, sodium hydroxide and a mixture of sodium carbonate and sodium hydroxide.
5. The manufacturing method of a lithium-titanium composite oxide doped with different metals of claim 1, wherein the titanium oxide is an anatase-type, or a titanium oxide hydrate
6. The manufacturing method of a lithium-titanium composite oxide doped with different metals of claim 1, wherein the lithium-containing compound is lithium hydroxide or lithium carbonate.
7. The manufacturing method of a lithium-titanium composite oxide doped with different metals of claim 1, wherein in the ii) process, water is used as a solvent, and the wet-pulverizing is performed using zirconia beads at 2000 to 4000 rpm.
8. The manufacturing method of a lithium-titanium composite oxide doped with different metals of claim 1, wherein in the iii) process, the spray drying is performed while inflowing hot air at a temperature of 250 to 300 °C
and discharging hot air at a temperature of 100 to 150 °C.
and discharging hot air at a temperature of 100 to 150 °C.
9. The manufacturing method of a lithium-titanium composite oxide doped with different metals of claim 1, wherein in the iv) process, the firing is performed by firing the spray-dried resultant of the iii) process at an air atmosphere at 700 to 800 °C for 5 h to 10.
10. The manufacturing method of a lithium-titanium composite oxide doped with different metals of claim 1, wherein the method further comprises v) pulverizing the fired particles in the iv) process.
11. The manufacturing method of a lithium-titanium composite oxide doped with different metals of claim 10, wherein the v) fired particles are pulverized using a jet air mill.
12. A lithium-titanium composite oxide doped with different metals comprising secondary particles formed by aggregating primary particles, having a spine] structure, and represented by the following chemical formula:
[Chemical Formula] Li4Ti5-(x+y)M x A y O12 in the chemical formula, the M is selected from the group consisting of Zr, Mg, Al, Ni, Co, Mn, and Cu, the A is selected from the group consisting of Na, K, and B, 0 1<=x<=1.5, 0<y<=1, x+y<=2, and 8<=x/y <=9.
[Chemical Formula] Li4Ti5-(x+y)M x A y O12 in the chemical formula, the M is selected from the group consisting of Zr, Mg, Al, Ni, Co, Mn, and Cu, the A is selected from the group consisting of Na, K, and B, 0 1<=x<=1.5, 0<y<=1, x+y<=2, and 8<=x/y <=9.
13. The lithium-titanium composite oxide doped with different metals of claim 12, wherein a diameter of the primary particles ranges from 0.5 µm to 0.8 µm and a diameter of the secondary particles ranges from 5 µm to 25 µm.
14. The lithium-titanium composite oxide doped with different metals of claim 12, wherein the lithium-titanium composite oxide doped with different metals has a main peak intensity of anatase-type TiO2 of less than or equal to 1, a main peak intensity of R-TiO2 of less than or equal to 1, and a main peak intensity of Li2TiO3 of less than or equal to 5 when a main peak intensity of Li4/3Ti5/3O4 is 100, wherein the main peak intensities are obtained from an X-ray powder diffractogram.
15. The lithium-titanium composite oxide doped with different metals of claim 12, wherein the different metal M is Zr and the different metal A is Na.
16. A positive electrode for a rechargeable lithium battery comprising the lithium-titanium composite oxide doped with different metals of claim 12.
17. A negative electrode for a rechargeable lithium battery comprising the lithium-titanium composite oxide doped with different metals of claim 12.
18. A rechargeable lithium battery comprising the positive electrode of claim 16.
19. A rechargeable lithium battery comprising the negative electrode of claim 17.
Applications Claiming Priority (3)
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| KR10-2013-0058563 | 2013-05-23 | ||
| KR1020130058563A KR101796233B1 (en) | 2013-05-23 | 2013-05-23 | Manufacturing method of lithium-titanium composite doped by different metal, and lithium-titanium composite doped with different metal made by same |
| PCT/KR2014/003060 WO2014189209A1 (en) | 2013-05-23 | 2014-04-09 | Manufacturing method of lithium-titanium composite oxide in which different metals are doped, and lithium-titanium composite oxide manufactured thereby in which different metals are doped |
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| EP (1) | EP3000787B1 (en) |
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| CN (1) | CN105531231B (en) |
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| KR101646601B1 (en) * | 2015-06-30 | 2016-08-10 | 한국원자력연구원 | Manufacturing method of titanium composite doped by different metal, and titanium composite doped with different metal made by same |
| KR101838235B1 (en) * | 2016-11-17 | 2018-03-13 | 주식회사 포스코이에스엠 | Manufacturing method of lithium-titanium complex oxide by particle size control using wet grinding |
| CN110199417A (en) * | 2016-11-22 | 2019-09-03 | 浦项化学有限公司 | Lithium-titanium composite oxide, preparation method and the lithium secondary battery comprising lithium-titanium composite oxide |
| JP7041806B2 (en) | 2017-03-13 | 2022-03-25 | エルジー エナジー ソリューション リミテッド | Negative electrode active material with high output characteristics and lithium secondary battery containing it |
| JP6837950B2 (en) * | 2017-09-21 | 2021-03-03 | 株式会社東芝 | Rechargeable batteries, battery packs, and vehicles |
| KR102090572B1 (en) * | 2018-03-12 | 2020-03-18 | (주)포스코케미칼 | Lithium-titanium composite oxide comprising primary particle doped by aluminum |
| KR101911219B1 (en) * | 2018-07-05 | 2018-10-24 | 주식회사 포스코이에스엠 | Manufacturing method of lithium titanium composite oxide, lithium titanium composite oxide manufactured by the same, and lithium secondary battery including the same |
| KR20200102882A (en) * | 2019-02-22 | 2020-09-01 | 주식회사 엘지화학 | Anode Active Material and Lithium Secondary Battery comprising the Same |
| KR102652332B1 (en) * | 2019-03-06 | 2024-03-27 | 주식회사 엘지에너지솔루션 | Anode Active Material and Lithium Secondary Battery comprising the Same |
| CN109879309B (en) * | 2019-03-14 | 2021-07-02 | 上海电气集团股份有限公司 | Preparation method of high-tap-density lithium titanate material |
| CN111900375B (en) * | 2020-06-30 | 2022-05-10 | 国网浙江省电力有限公司湖州供电公司 | Preparation method of long-life negative electrode material for power energy storage and application of long-life negative electrode material in lithium ion battery |
| KR102581795B1 (en) * | 2020-12-24 | 2023-09-22 | 주식회사 에코프로비엠 | Method for preparing positive active material for lithium secondary battery using waste positive acive material |
| SE2250523A1 (en) * | 2022-04-29 | 2023-10-30 | Tiotech As | A battery material and its manufacture |
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| JP2002145619A (en) | 2000-09-04 | 2002-05-22 | Mitsubishi Chemicals Corp | Lithium manganese multiple oxide, positive electrode material for lithium secondary cell, positive electrode for lithium secondary cell and manufacturing method of lithium secondary cell and lithium manganese multiple oxide |
| JP2005339887A (en) * | 2004-05-25 | 2005-12-08 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| US7632276B2 (en) * | 2004-07-29 | 2009-12-15 | Greatbatch Medical Sa | Minimally invasive collapsible surgical reamer |
| FR2874603B1 (en) * | 2004-08-31 | 2006-11-17 | Commissariat Energie Atomique | MIXED TITANIUM AND DENSE LITHIUM MIXED OXIDE POWDER COMPOUND, PROCESS FOR PRODUCING THE SAME, AND ELECTRODE COMPRISING SUCH COMPOUND |
| JP4249727B2 (en) * | 2005-05-13 | 2009-04-08 | 株式会社東芝 | Nonaqueous electrolyte battery and lithium titanium composite oxide |
| US7879493B2 (en) * | 2006-06-05 | 2011-02-01 | A123 Systems, Inc. | Alkali metal titanates and methods for their synthesis |
| KR101064093B1 (en) * | 2009-07-28 | 2011-09-08 | 콘티넨탈 오토모티브 시스템 주식회사 | Fastening structure of printed circuit board and housing |
| CN102122710B (en) * | 2009-08-18 | 2014-08-20 | 成都兴能新材料有限公司 | Zr-doped lithium titanate electrode material and preparation method thereof |
| JP2011113795A (en) * | 2009-11-26 | 2011-06-09 | Nippon Chem Ind Co Ltd | Manufacturing method of lithium titanate for lithium secondary battery active material |
| KR101503433B1 (en) * | 2010-04-13 | 2015-03-24 | 주식회사 포스코이에스엠 | Manufacturing method of lithium-titanium composite comprising carbon in crystal, lithium-titanium composite comprising carbon in crystal made by the same, and the use of the same |
| CN101986445A (en) * | 2010-05-12 | 2011-03-16 | 罗劲松 | Method for producing lithium battery cathode material lithium titanate |
| JP5450284B2 (en) * | 2010-06-28 | 2014-03-26 | 株式会社日立製作所 | Lithium titanate particles and manufacturing method thereof, negative electrode for lithium ion battery, and lithium battery |
| CN102054963A (en) * | 2010-07-22 | 2011-05-11 | 中信国安盟固利动力科技有限公司 | Titanium acid lithium battery cathode material containing rare metal elements |
| KR20120017991A (en) * | 2010-08-20 | 2012-02-29 | 삼성에스디아이 주식회사 | Negative active material for rechargeable lithium battery, method of preparing same, and rechargeable lithium battery including same |
| JP5671969B2 (en) * | 2010-11-24 | 2015-02-18 | 日立化成株式会社 | Lithium titanium compound particles and method for producing the same, electrode material for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
| CN103066265B (en) * | 2011-10-24 | 2015-03-04 | 中国科学院物理研究所 | Sodium ion battery negative pole active substance and preparation method and application thereof |
| JP2013095646A (en) * | 2011-11-02 | 2013-05-20 | Taiyo Yuden Co Ltd | Lithium-titanium complex oxide, and battery electrode and lithium ion secondary battery using the same |
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| EP3000787A4 (en) | 2016-11-30 |
| WO2014189209A1 (en) | 2014-11-27 |
| EP3000787A1 (en) | 2016-03-30 |
| CN105531231B (en) | 2018-02-16 |
| KR101796233B1 (en) | 2017-12-01 |
| CA2913121A1 (en) | 2014-11-27 |
| US20160079594A1 (en) | 2016-03-17 |
| EP3000787B1 (en) | 2020-02-12 |
| KR20140137720A (en) | 2014-12-03 |
| JP2016523797A (en) | 2016-08-12 |
| JP6204576B2 (en) | 2017-09-27 |
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